Quaternary fatty acid triethanolamine ester salts and their use as fabric softeners

ABSTRACT

The present invention relates to biodegradable softener compounds of the formula (1): [(R) 4-m —N( + )—[(CH 2 ) n —Y—R 1 ] m ]X( − ) with an acid value of no more than 6.5. A process for making said compound is also provided. The softener can be incorporated into softener compositions to form solid and liquid compositions, including liquid dispersions and clear compositions.

TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to fabric softening compounds andcomposition thereof useful for softening fabrics. It especially relatesto fabric softening compounds and/or compositions suitable forformulating textile softening compositions for use in the rinse cycle ofa textile laundering operation to provide excellentfabric-softening/static-control benefits, the compositions beingcharacterised by, e.g., reduced staining of fabric, excellent waterdispersibility, rewettability, and/or storage and viscosity stability atsub-normal temperatures, i.e., temperatures below normal roomtemperature, e.g., 25° C. The compositions of the invention arepreferably liquid softening compositions, and more preferably,translucent or clear liquid softening compositions.

BACKGROUND OF THE INVENTION

[0002] Clear softening compositions are known in the art. For example,EP-A-0,404,471 discloses clear softening compositions with at least 20%by weight softener and at least 5% by weight of a short chain organicacid.

[0003] Formulating softening compositions which are clear is however notthe only condition required of softening compositions. Indeed, suchcompositions are expected to provide an effective softening performanceon the treated fabric. In this respect, EP-A-0,550,361 disclosessoftening compounds with specific molar ratios of fatty acid fraction totertiary amine which provide effective softening performance withoutbeing detrimental to the fluidity and stability of compositioncontaining said compound.

[0004] It is now an object to provide a softening compound whichprovides effective softening performance.

[0005] Still another object of the invention, is to provide acomposition containing said compound which are clear but still notdetrimental to the fluidity and stability of composition.

[0006] These objects have now surprisingly been met by producing thesoftening compound from the condensation of fatty acids withtriethanolamine, wherein the condensation occurs for a period such thatthe condensation product has an acid value (AV) of less than 6.5, thecondensation product subsequently being quaternized.

[0007] The AV of the compound is measured on the condensation productbefore the quaternisation step by the test method defined hereinafter.

[0008] For optimum softness benefit, it is preferred that the reactantsare present in a molar ratio of fatty acid fraction to triethanolamineof from 1:1 to 2.5:1.

[0009] The finding that a lower acid value of the invention compoundleads to higher softness performance when using the invention compoundis very surprising and unexpected. Indeed, as known from GB 2,039,556,the addition of fatty acid provide an increase in the softnessperformance of the softening composition. The Applicant, in thisrespect, has found that the addition of fatty acid, instead ofdecreasing the acid value, increased the acid value. Accordingly, it wasgenerally believed that the softness performance in relation to the acidvalue followed a curve showing a maximum at an AV above 10. To thecontrary, it has been found that the softness performance followed aline whereby the higher the acid value, the less softening performanceis obtained.

[0010] By effective softening performance, it is meant that the compoundof the present invention provides better softening performance tofabrics compared to fabrics which have been treated with a similarcompound but with an AV above 6.5. In a preferred embodiment, thecompound of the invention provides better softness performance ontreated fabrics therewith compared to compounds having the hereinbelowdescribed molar ratios but not the specified AV.

SUMMARY OF THE INVENTION

[0011] The present invention relates to a biodegradable fabric softenercompound comprising a quaternary ammonium salt, the quaternised ammoniumsalt being a quaternised product of condensation between:

[0012] a)-a fraction of saturated or unsaturated, linear or branchedfatty acids, or of derivatives of said acids, said fatty acids orderivatives each possessing a hydrocarbon chain in which the number ofatoms is between 5 and 21, and

[0013] b)-triethanolamine, characterised in that said condensationproduct has an acid value, measured by titration of the condensationproduct with a standard KOH solution against a phenolphtaleineindicator, of less than 6.5.

[0014] In a preferred embodiment of the invention, the fatty acidfraction and the triethanolamine are present in a molar ratio of from1:1 to 2.5:1.

[0015] The present invention also relates to a process for making asoftener compound, and in particular said compound.

[0016] Also provided herein is a softening composition containing saidsoftening compound.

DETAILED DESCRIPTION OF THE INVENTION

[0017] I-Softener Compound

[0018] The essential component of the invention is a biodegradablefabric softener compound comprising a quaternary ammonium salt, thequaternised ammonium salt being a quaternised product of condensationbetween:

[0019] a)-a fraction of saturated or unsaturated, linear or branchedfatty acids, or of derivatives of said acids, said fatty acids orderivatives each possessing a hydrocarbon chain in which the number ofatoms is between 5 and 21, and

[0020] b)-triethanolamine,

[0021] characterised in that said condensation product has an acidvalue, measured by titration of the condensation product with a standardKOH solution against a phenolphtaleine indicator, of less than 6.5.

[0022] The acid value is preferably less than or equal to 5, morepreferably less than 3. Indeed, the lower the AV, the better softenesssoftness performance is obtained.

[0023] The acid value is determined by titration of the condensationproduct with a standard KOH solution against a phenolphtaleine indicatoraccording to ISO#53402. The AV is expressed as mg KOH/g.

[0024] For optimum softness benefit, it is preferred that the reactantsare present in a molar ratio of fatty acid fraction to triethanolamineof from 1:1 to 2.5:1.

[0025] It has also been found that the optimum softness performance isalso affected by the detergent carry-over laundry conditions, and moreespecially by the presence of the anionic surfactant in the solution inwhich the softening composition is used. Indeed, the presence of anionicsurfactant that is usually carried over from the wash will interact withthe softener compound, thereby reducing its performance. Thus, dependingon usage conditions, the mole ratio of fatty acid/triethanolamine can becritical. Accordingly, where no rinse occurs between the wash cycle andthe rinse cycle containing the softening compound, a high amount ofanionic surfactant will be carried over in the rinse cycle containingthe softening compound. In this instance, it has been found that a fattyacid fraction/triethanolamine mole ratio of 1.4:1 to 1.8:1 is preferred.By high amount of anionic surfactant, it is meant that the presence ofanionic in the rinse cycle at a level such that the molar ratio anionicsurfactant/cationic softener compound of the invention is at least 1/10.

[0026] Thus, according to another aspect of the invention, there isprovided a method of treating fabrics which comprises the step ofcontacting the fabrics in an aqueous medium containing the softenercompound of the invention or softening composition thereof wherein thefatty acid/triethanolamine mole ratio in the softener compound is from1.4:1 to 1.8:1, preferably 1.5:1 and the aqueous medium comprises amolar ratio of anionic surfactant to said softener compound of theinvention of at least 1:10.

[0027] Where, on the other hand, an intermediate rinse cycle occursbetween the wash and the later rinse cycle, less anionic surfactant,i.e. less than 1:10 of a molar ratio anionic surfactant to cationiccompound of the invention, will then be carried over. Accordingly, ithas been found that a fatty acid/triethanolamine mole ratio of 1.8:1 to2.2:1 is then preferred. Accordingly, in another aspect of theinvention, there is provided a method of treating fabrics whichcomprises the step of contacting the fabrics in an aqueous mediumcontaining the softener compound of the invention or softeningcomposition thereof wherein the fatty acid/triethanolamine mole ratio inthe softener compound is from 1.8:1 to 2:1, preferably 2.0:1 and theaqueous medium comprises a molar ratio of anionic surfactant to saidsoftener compound of the invention of less than 1:10.

[0028] Preferred compounds of the invention include compounds having theformula:

[0029] wherein each R substituent is hydrogen or a short chain C₁-C₆alkyl or hydroxyalkyl group; preferably C₁-C₃ alkyl or hydroxyalkylgroup, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, andthe like, benzyl, or mixtures thereof;

[0030] each m is in the range of 1 to 2.5:

[0031] each n is from 1 to 4; preferably 2;

[0032] each Y is —O—(O)C—, —(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—;preferably —O—(O)C—; the sum of carbons in each R¹, plus one when Y is—O—(O)C— or —(R)N—(O)C— (“YR¹ sum”), is C₆-C₂₂, preferably C₁₂₋₂₂, morepreferably C₁₄-C₂₀, (hereinafter, R¹ and YR¹ are used interchangeably torepresent the hydrophobic chain, the R¹ chain lengths in general beingeven numbered for fatty alcohols and odd for fatty acids), but no morethan one R¹, or YR¹, sum being less than 12 and then the other R¹, orYR¹, sum is at least 16, with each R¹ comprising a long chain C₅-C₂₁ (orC₆-C₂₂), branched alkyl or unsaturated alkyl, preferably C₁₀-C₂₀ (orC₉-C₁₉) branched alkyl or unsaturated alkyl, most preferably C₁₂-C₁₈ (orC₁₁-C₁₇) branched alkyl, or unsaturated alkyl, optionally substituted,

[0033] For the unsaturated alkyl group, the Iodine Value of the parentfatty acid of this R¹ group is from 0 to 140, more preferably when usedin clear softening composition the Iodine Value of the parent fatty acidof this R¹ group is from 50 to 130; whilst when used in dispersion theIodine Value of the parent fatty acid of this R¹ group is preferablyfrom 0 to 70 (As used herein, the “branched alkyl” groups include thosethat contain a substituent that is hydrophobic, even though they areattached to the main chain by bonds that are not carbon to carbon, e.g.,by oxygen, as in the alkoxy substituents, and the Iodine Value of a“parent” fatty acid, or “corresponding” fatty acid, is used to define alevel of unsaturation for an R¹ groups that is the same as the level ofunsaturation that would be present in a fatty acid containing the sameR¹ group. When an individual R¹ is both branched and unsaturated, it istreated as if it is branched.); and

[0034] wherein the counterion, X⁻, can be any softener-compatible anion;preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,and/or nitrate, more preferably methylsulfate.

[0035] Also suitable as softener compounds according to the inventionare those that are prepared as a single compound from blends of all thedifferent branched and unsaturated fatty acids that are represented(total fatty acid blend), rather than from blends of mixtures ofseparate finished softener compound that are prepared from differentportions of the total fatty acid blend.

[0036] It is preferred that at least a substantial percentage of thefatty acyl groups are unsaturated, e.g., from 25% to 70%, preferablyfrom 50% to 65%. Polyunsaturated fatty acid groups can be used. Thetotal level of active containing polyunsaturated fatty acyl groups (TPU)can be from 3% to 30%, preferably from 5% to 25%, more preferably from10% to 18%. Both cis and trans isomers can be used, preferably with acis/trans ratio of from 1:1 to 50:1, the minimum being 1:1, preferablyat least 3:1, and more preferably from 4:1 to 20:1. (As used herein, the“percent of softener active” containing a given R¹ group is the same asthe percentage of that same R¹ group is to the total R¹ groups used toform all of the softener actives.)

[0037] The mixed branched-chain and unsaturated materials are easier toformulate than conventional saturated branched chain fabric softenercompounds. They can advantageously be used to form clear or translucentcompositions.

[0038] II-Process for Making Said Compound

[0039] Another essential feature of the invention is a process formaking a softener compound, in particular the softener compounds of theinvention. This include the steps of

[0040] a)-reacting the fatty acid fraction comprising fatty acids offormula R¹ COOH in which R¹ is a long chain C₅-C₂₁ branched alkyl orunsaturated alkyl, optionally substituted, with at least atriethanolamine, for a period such that the condensation productobtained compound has an acid value, measured by titration of thecondensation product with a standard KOH solution against aphenolphtaleine indicator according to ISO#53402, of less than 6.5, and

[0041] b)-reacting the condensation product thereby obtained with analkylating agent, in the presence or absence of a solvent.

[0042] By fatty acid fraction, it is meant a mixture having fatty acids,fatty acid esters or mixtures therefore. This mixture can be eithercommercially available or provided by the reacting of a source oftriglycerides. By reacting, it is meant the process of:

[0043] (a) hydrogenating a triglyceride product comprising a mixture ofcompounds of the formula (1)

R¹—OCH₂—CHO(—R²)—CH₂0—R³  (1)

[0044] wherein R¹, R² and R³ are acyl groups of which at least 1%contain 16 carbon atoms, and at least 70% contain 18 carbon atoms,provided that said acyl groups containing 18 carbon atoms includepredominantly mono unsaturated acyl groups and minor amounts ofsaturated, diunsaturated and triunsaturated acyl groups, underhydrogenation conditions whereunder diunsaturated and triunsaturatedacyl groups containing 18 carbon atoms are hydrogenated provided thatformation of saturated acyl groups containing 18 carbon atoms isminimized;

[0045] (b) hydrolyzing the hydrogenated product of step (a) to formglycerine and a mixture of fatty acids based on said acyl groups.

[0046] The triglyceride source is preferably derived from vegetable oilsand/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, etc and mixtures of these oils. One highly preferredtriglyceride source which can be used herein is canola oil. Canola oilis a mixture of triglycerides having an appropriate chain lengthdistribution and degree of unsaturation of the respective acyl groups.Canola oil is a particularly desirable starting product in accordancewith the process of the present invention, for several reasons. Inparticular, its natural distribution of the chain lengths of therespective acyl groups has a notably high proportion of acyl groupscontaining 18 carbon atoms, thus avoiding the additional expenseincurred when using other commercial sources of C₁₈ fatty acids asstarting materials.

[0047] The triglyceride starting product can be hydrogenated, ifdesired, to convert diunsaturated and triunsaturated acyl groups,particularly those containing 18 carbon atoms, to their monounsaturatedcounterparts. It is normally desirable that hydrogenation ofmono-unsaturated acyl groups is minimized and even completely avoided.Saturated acyl groups can be obtained from normally saturated sourcesand mixed with unsaturated acyl groups. In some useful mixtures of acylgroups, no more than 10% of unsaturated C₁₈ acyl groups are hydrogenatedto their saturated counterparts. For some products, hydrogenation ofdiunsaturated and triunsaturated C₁₈ acyl groups is preferablymaximized, consistent with minimal formation of saturated C₁₈ groups.For instance, triunsaturated acyl groups can be completely hydrogenatedwithout achieving complete hydrogenation of diunsaturated acyl groups.

[0048] Hydrogenation of the triglyceride starting product whichmaximizes monounsaturated acyl groups can be readily achieved bymaintaining an appropriate balance of the conditions of thehydrogenation reaction. The process variables in the hydrogenation oftriglycerides and the effects of altering such variables, are generallyquite familiar to those of ordinary skill in this art. In general,hydrogenation of the triglyceride starting product can be carried out ata temperature ranging (broadly stated) between 170° C. and 205° C. andmore preferably within a somewhat narrower range of from 185° C. to 195°C. The other significant process variable is the pressure of hydrogenwithin the hydrogenation reactor. In general, this pressure should bemaintained within a range (broadly stated) of from 2 psig to 20 psig,and more preferably between from 5 psig and 15 psig.

[0049] Within these ranges of parameters, hydrogenation can be carriedout with a particular view to the effects of these parameters. Lowerhydrogen pressures in the reactor permit a greater degree of control ofthe reaction, particularly as to its selectivity. By “selectivity” ismeant the hydrogenation of diunsaturated and triunsaturated acyl groupswithout excessive hydrogenation of mono unsaturated acyl groups. On theother hand, higher hydrogen pressures afford less selectivity.Selectivity can be desirable in certain instances.

[0050] Higher hydrogenation temperatures are associated with fasterrates of hydrogenation and with greater selectivity of thehydrogenation. Conversely, lower hydrogenation temperatures areassociated with less selectivity (i.e. increased hydrogenation of themono unsaturated groups), and particularly with slower hydrogenationrates in general.

[0051] These considerations are also balanced with considerations ofstereochemistry. More specifically, the presence of unsaturation in theacyl groups can lead to the formation of different stereoisomers in theacyl groups upon hydrogenation. The two possible stereoisomericconfigurations for unsaturated fatty acyl groups are known as the “cis”and the “trans” forms. The presence of the cis form is preferred, as itis associated with a lower melting point of the eventual product and,thus with greater fluidity, and better low temperature phase stabilityof clear compositions. Thus, another reason that canola oil is aparticularly preferred triglyceride starting product is that, as anaturally occurring material, the acyl groups present in thistriglyceride exhibit only the cis form. In the hydrogenation, higherhydrogen pressures are associated also with a decreased tendency of theacyl group to undergo configuration change from the cis form to thetrans form. Also, higher hydrogenation temperatures while favorable forsome reasons are also associated with higher conversion of cisunsaturation to the trans form. Products exhibiting satisfactoryproperties can be obtained by appropriate control of the hydrogenationconditions so as to afford both selectivity and control of thestereochemical configurations of the product.

[0052] The hydrogenation is carried out in the presence of a suitablehydrogenation catalyst. Such catalysts are well known and commerciallyavailable. They generally comprise nickel, palladium, ruthenium orplatinum, typically on a suitable catalyst support. A suitable catalystis a nickel based catalyst such as sold by Engelhard under the tradedesignation “N-545” ®.

[0053] In one variation, the hydrogenation is carried out to an endpoint at which hydrogenation of the diunsaturation and triunsaturationin the triglyceride product is maximized, while formation of saturatedacyl groups is minimized. The progress of the hydrogenation reactiontoward the end point can readily be monitored by periodic measurement ofthe iodine value of the reaction mass. As the hydrogenation proceeds,the Iodine Value decreases. For example, the hydrogenation reaction canbe discontinued when the Iodine Value reaches 95.

[0054] Other requirements for hydrogenation reactions are well known,such as the types of reactor, cooling means to maintain the desiredtemperature, the provision of means for agitation effective to provideadequate contact between the triglyceride and the hydrogen and catalyst,etc.

[0055] The triglyceride containing the desired acyl groups is reacted,typically by hydrolyzing or transesterification, to obtain the desiredfatty acyl groups as, e.g., the corresponding fatty acids and/or fattyacid esters. That is, the three ester bonds in the triglyceride arebroken so that the hydrogenated combination of acyl groups is convertedto a mixtures of fatty acids and/or esters having the same chain lengthdistribution as in the acyl groups, and having the distribution ofsaturation and unsaturation provided by the hydrogenation reaction.

[0056] Hydrolysis can be carried out under any of the suitableconditions known in this art for hydrolysis of triglycerides into theirfatty acid constituents. In general, the triglyceride is reacted withhigh temperature steam in a reactor, wherein the fatty acids are splitoff from glycerine, following which the steam is condensed to form anaqueous solution of glycerine and this solution is removed.Transesterification of the triglyceride can be carried out under any ofthe suitable conditions known in this art for transesterification oftriglycerides into their fatty acid ester constituents.

[0057] Once the fatty acid fraction is obtained, according to step a) ofthe invention process, it is reacted (or also called esterified) withtriethanolamine for a period such that the condensation product obtainedcompound has an acid value (AV), measured by measured by titration ofthe condensation product with a standard KOH solution against aphenolphtaleine indicator according to ISO#53402, of less than 6.5.

[0058] For optimum softness benefit, it is preferred that the reactantsare present in a molar ratio of fatty acid to triethanolamine of from1:1 to 2.5:1. More preferably, the reactants are present in a molarratio of fatty acid fraction to triethanolamine of from 1.4:1 to lessthan 1.8:1, preferably 1.5:1 when the aqueous medium in which they areto be used comprises a molar ratio of anionic surfactant to saidsoftener compound of the invention of at least 1:10.

[0059] On the other hand, when the aqueous medium in which they are tobe used comprises a molar ratio of anionic surfactant to said softenercompound of the invention of less than 1:10, the reactants arepreferably present in a molar ratio of fatty acid fraction totriethanolamine of from 1.8:1 to 2.2:1, preferably 2.0:1.

[0060] The esterification is carried out under conventionalesterification conditions, providing an acidic catalyst and providingfor withdrawal of byproduct water of condensation. Preferably, a smallamount generally up to 1.0 wt. % of the reactant (i.e. acids and amine),of hypo phosphorous acid (HPPA) is added to the esterification reactionmixture. The HPPA is believed to catalyze the reaction and as well topreserve or even improve the color of the product obtained in thisreaction. Indeed, color control is critical to the appearance of clearsoftening compositions. Preferably, esterification is allowed to proceedcompletely such that all amine present is esterified with the fatty acidfraction. The Av is measured at different time interval on theesterified reaction product and the condensation reaction (also calledesterification reaction) is not stopped until the required AV isreached. This AV determination is made according to the ISO definedherein before.

[0061] After the required acid value for the condensation product hasbeen obtained, it is, according to step b) of the invention process,reacted with an alkylating agent, in the presence or absence of asolvent.

[0062] The alkylation (also called quaternisation step) is carried outunder conditions and with reactants generally familiar to thoseexperienced in this field. The quaternizing agent has the formula QA,wherein Q is preferably methyl, benzyl, or ethyl, and A is an inertmonovalent anion.

[0063] Preferably, the alkylating agent is selected from alkyl halides,sulphates, phosphates and carbonates, more preferably alkyl halides andsulphates.

[0064] Suitable alkyl halide compounds for use as alkylating agents inthe present invention are selected from methyl chloride, benzylchloride. Suitable alkyl sulphate compounds for use as alkylating agentsin the present invention are the polyalkylsulphates selected fromdimethylsulphate and diethylsulphate. One of the more preferredalkylating agent is dimethylsulfate.

[0065] This alkylation step produces the quaternary ammonium ester ofthe invention.

[0066] When the softener compound of the invention is formulated intoclear or translucent compositions, it is most preferred to drive thequaternising reaction as far to completion as possible, for the bestclarity of the finished composition. This is most particularly desirablewhen a high perfume level in the composition is present, e.g of morethan 1.5% by weight of the composition of perfume and typically of 2.5%by weight. Such completion reaction can typically be done though longerreaction times, controlling temperatures and pressures, and using excessalkylating agent in the reaction. It is also most preferred to removeunreacted alkylating agent upon completion of the reaction to avoidmalodor and also potential safety issues (e.g. methyl chloride may beremoved by vacuum stripping).

[0067] C-Fabric Softening Composition

[0068] The compound of the invention is preferably incorporated in afabric softening composition. Typical levels of incorporation are offrom 1% to 80% by weight, preferably from 5% to 75%, more preferablyfrom 15% to 70%, and even more preferably from 19% to 65%, by weight ofthe composition. Of course, mixtures of the above defined compound canbe used herein.

[0069] The softening composition according to the present invention canbe in different form such as in liquid or solid form as definedhereinafter.

[0070] When formulated as a liquid fabric softening composition, thecomposition may be in the form of a dispersion, e.g. aqueous dispersion,or also in the form of a clear composition. Accordingly, when in liquidform, the composition in addition to the softening compound of theinvention will also preferably comprises optional ingredients. When insuch liquid forms, it has been found most preferred, in order to improvethe stability of the softening composition according to the invention,that the softening compositions have a pH of from 3 to 4.

[0071] III. OPTIONAL INGREDIENTS

[0072] (A)-Principal Solvent

[0073] A principal solvent is one of the preferred optional ingredientfor use in the present composition invention. The compositions of thepresent invention may comprise a principal solvent system. This isparticularly the case when formulating liquid, clear fabric softeningcompositions. When employed, the principal solvent is typically used ata level of less than 40% by weight, preferably from 6% to 35%, morepreferably from 8% to 25%, and even more preferably from 10% to 20%, byweight of the composition. The principal solvent is selected to minimizesolvent odor impact in the composition and to provide a low viscosity tothe final composition. For example, isopropyl alcohol is not veryeffective and has a strong odor. n-Propyl alcohol is more effective, butalso has a distinct odor. Several butyl alcohols also have odors but canbe used for effective clarity/stability, especially when used as part ofa principal solvent system to minimize their odor. The alcohols are alsoselected for optimum low temperature stability, that is they are able toform compositions that are liquid with acceptable low viscosities andtranslucent, preferably clear, down to about 40° F. (about 4.4° C.) andare able to recover after storage down to about 20° F. (about 6.7° C.).

[0074] The suitability of any principal solvent for the formulation ofthe liquid, concentrated, preferably clear, fabric softener compositionsherein with the requisite stability is surprisingly selective. Suitablesolvents can be selected based upon their octanol/water partitioncoefficient (P). Octanol/water partition coefficient of a principalsolvent is the ratio between its equilibrium concentration in octanoland in water. The partition coefficients of the principal solventingredients of this invention are conveniently given in the form oftheir logarithm to the base 10, logP.

[0075] The logP of many ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), Irvine, Calif., contains many, along with citationsto the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each ingredient, and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding.These ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are preferably used insteadof the experimental logP values in the selection of the principalsolvent ingredients which are useful in the present invention. Othermethods that can be used to compute ClogP include, e.g., Crippen'sfragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21(1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf.Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J.Med. Chem.—Chim. Theor., 19, 71 (1984). The principal solvents hereinare selected from those having a ClogP of from about 0.15 to about 0.64,preferably from about 0.25 to about 0.62, and more preferably from about0.40 to about 0.60, said principal solvent preferably being at leastsomewhat asymmetric, and preferably having a melting, or solidification,point that allows it to be liquid at, or near room temperature. Solventsthat have a low molecular weight and are biodegradable are alsodesirable for some purposes. The more assymetric solvents appear to bevery desirable, whereas the highly symmetrical solvents such as1,7-heptanediol, or 1,4-bis(hydroxymethyl) cyclohexane, which have acenter of symmetry, appear to be unable to provide the essential clearcompositions when used alone, even though their ClogP values fall in thepreferred range.

[0076] The most preferred principal solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

[0077] Operable principal solvents are disclosed and listed below whichhave ClogP values which fall within the requisite range. These includemono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. These principal solvents are all disclosed in WO97/03169 having the title “CONCENTRATED, STABLE, PREFERABLY CLEAR,FABRIC SOFTENING COMPOSITION”.

[0078] Particularly preferred principal solvents include hexanediolssuch as 1,2-hexanediol; and C8 diols such as 2-ethyl-1,3-hexanediol and2,2,4-trimethyl-1,3-pentanediol, ethoxylates of2,2,4-trimethyl-1,3-pentanediol and ethoxylates of2-ethyl-1,3-hexanediol; and 1,2 cyclohexanedimethanol.

[0079] Mixtures of principal solvent can also be used for the purpose ofthe present invention.

[0080] The principal solvents are desirably kept to the lowest levelsthat are feasible in the present compositions for obtaining translucencyor clarity. The presence of water exerts an important effect on the needfor the principal solvents to achieve clarity of these compositions. Thehigher the water content, the higher the principal solvent level(relative to the softener level) is needed to attain product clarity.Inversely, the less the water content, the less principal solvent(relative to the softener) is needed. Thus, at low water levels of from5% to 15%, the softener active-to-principal solvent weight ratio ispreferably from 55:45 to 85:15, more preferably from 60:40 to 80:20. Atwater levels of from 15% to 70%, the softener active-to-principalsolvent weight ratio is preferably from 45:55 to 70:30, more preferablyfrom 55:45 to 70:30. But at high water levels of from 70% to 80%, thesoftener active-to-principal solvent weight ratio is preferably from30:70 to 55:45, more preferably from 35:65 to 45:55. At even higherwater levels, the softener to principal solvent ratios should also beeven higher.

[0081] The compositions can also inherently provide improved perfumedeposition of certain perfume components, especially for those that arepoorly fabric substantive as compared to conventional fabric softeningcompositions, especially when the perfume is added to the compositionsat, or near, room temperature.

[0082] More preferred for use herein is a combination of principalsolvents. Most preferred combinations are2,2,4-trimethyl-1,3-pentanediol (TMPD) in combination with 1,2hexanediol. With the above preferred combinations, lower total levels ofsolvents can be achieved thereby reducing the overall cost of theformulation. By the present principal solvent combinations, it has beenfound that the resulting products have surprising phase stability andfully recover from freezing down to 0° F. (−18° C.). The resultingproducts have also been surprisingly found to have excellent waterdispersibility. Furthermore, another advantage with the use of suchcombination is their large availibility.

[0083] (B)

[0084] Low molecular weight water soluble solvents can also be used atlevels of from 0% to 12%, preferably from 1% to 10%, more preferablyfrom 2% to 8% by weight. The water soluble solvents cannot provide aclear product at the same low levels of the principal solvents describedhereinbefore but can provide clear product when the principal solvent isnot sufficient to provide completely clear product. The presence ofthese water soluble solvents is therefore highly desirable. Suchsolvents include: ethanol; isopropanol; 1,2-propanediol;1,3-propanediol; propylene carbonate; 1,4-cyclohexanedimethanol; etc.but do not include any of the principal solvents (A). These watersoluble solvents have a greater affinity for water in the presence ofhydrophobic materials like the softener compound than the principalsolvents.

[0085] Among the above described co-solvent to be used in combinationwith the principal solvent, 1,4 cyclohexanedimethanol is a preferredco-solvent.

[0086] (C) Brighteners

[0087] The compositions herein can also optionally contain from 0.005%to 5% by weight of certain types of hydrophilic optical brightenerswhich also provide a dye transfer inhibition action. If used, thecompositions herein will preferably comprise from 0.001% to 1% by weightof such optical brighteners.

[0088] The hydrophilic optical brighteners useful in the presentinvention are those having the structural formula:

[0089] wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

[0090] When in the above formula, R¹ is anilino, R₂ isN-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the rinse added compositions herein.

[0091] When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.

[0092] When in the above formula, R₁ is anilino, R₂ is morphilino and Mis a cation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.

[0093] (D) Dispersibility Aids

[0094] Relatively concentrated compositions containing both saturatedand unsaturated diester quaternary ammonium compounds can be preparedthat are stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixturesthereof. These aids are described in P&G Copending Application Ser. No.08/461,207, filed Jun. 5, 1995, Wahl et al., specifically on page 14,line 12 to page 20, line 12, which is herein incorporated by reference.When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (1), e.g., the mono-long chain alkyl cationic surfactantand/or the fatty acid which are reactants used to form the biodegradablefabric softener active as discussed hereinbefore, or added as a separatecomponent. The total level of dispersibility aid includes any amountthat may be present as part of component (I).

[0095] (1) Mono-Alkyl Cationic Quaternary Ammonium Compound

[0096] When the mono-alkyl cationic quaternary ammonium compound ispresent, it is typically present at a level of from 2% to 25%,preferably from 3% to 17%, more preferably from 4% to 15%, and even morepreferably from 5% to 13% by weight of the composition, the totalmono-alkyl cationic quaternary ammonium compound being at least at aneffective level.

[0097] Such mono-alkyl cationic quaternary ammonium compounds useful inthe present invention are, preferably, quaternary ammonium salts of thegeneral formula:

[R⁴N+(R⁵)₃] X⁻

[0098] wherein

[0099] R⁴ is C₈-C₂₂ alkyl or alkenyl group, preferably C₁₀-C₁₈ alkyl oralkenyl group; more preferably C₁₀-C₁₄ or C₁₆-C₁₈ alkyl or alkenylgroup;

[0100] each R⁵ is a C₁-C₆ alkyl or substituted alkyl group (e.g.,hydroxy alkyl), preferably C₁-C₃ alkyl group, e.g., methyl (mostpreferred), ethyl, propyl, and the like, a benzyl group, hydrogen, apolyethoxylated chain with from 2 to 20 oxyethylene units, preferablyfrom 2.5 to 13 oxyethylene units, more preferably from 3 to 10oxyethylene units, and mixtures thereof; and

[0101] X⁻ is as defined hereinbefore for (Formula (I)).

[0102] Especially preferred dispersibility aids are monolauryl trimethylammonium chloride and monotallow trimethyl ammonium chloride availablefrom Witco under the trade names Adogen® 412 and Adogen® 471, monooleylor monocanola trimethyl ammonium chloride available from Witco under thetradename Adogen(® 417, monococonut trimethyl ammonium chlorideavailable from Witco under the trade name Adogen® 461, and monosoyatrimethyl ammonium chloride available from Witco under the trade nameAdogen® 415.

[0103] The R⁴ group can also be attached to the cationic nitrogen atomthrough a group containing one, or more, ester, amide, ether, amine,etc., linking groups which can be desirable for increasedconcentratability of component (I), etc. Such linking groups arepreferably within from one to three carbon atoms of the nitrogen atom.

[0104] Mono-alkyl cationic quaternary ammonium compounds also includeC₈-C₂₂ alkyl choline esters. The preferred dispersibility aids of thistype have the formula:

R¹C(O)—O—CH₂CH₂N+(R)₃X⁻

[0105] wherein R¹, R and X⁻ are as defined previously.

[0106] Highly preferred dispersibility aids include C₁₂-C₁₄ coco cholineester and C₁₆-C₁₈ tallow choline ester.

[0107] Suitable biodegradable single-long-chain alkyl dispersibilityaids containing an ester linkage in the long chains are described inU.S. Pat. No. 4,840,738, Hardy and Walley, issued Jun. 20, 1989, saidpatent being incorporated herein by reference.

[0108] When the dispersibility aid comprises alkyl choline esters,preferably the compositions also contain a small amount, preferably from2% to 5% by weight of the composition, of organic acid. Organic acidsare described in European Patent Application No. 404,471, Machin et al.,published on Dec. 27, 1990, supra, which is herein incorporated byreference. Preferably the organic acid is selected from the groupconsisting of glycolic acid, acetic acid, citric acid, and mixturesthereof.

[0109] Ethoxylated quaternary ammonium compounds which can serve as thedispersibility aid include ethylbis(polyethoxy ethanol)alkylammoniumethyl-sulfate with 17 moles of ethylene oxide, available under the tradename Variquat® 66 from Witco Corporation; polyethylene glycol (15)oleammonium chloride, available under the trade name Ethoquad® 0/25 fromAkzo; and polyethylene glycol (15) cocomonium chloride, available underthe trade name Ethoquad® C/25 from Akzo.

[0110] Quaternary compounds having only a single long alkyl chain, canprotect the cationic softener from interacting with anionic surfactantsand/or detergent builders that are carried over into the rinse from thewash solution.

[0111] (2) Nonionic Surfactant (Alkoxylated Materials)

[0112] Suitable nonionic surfactants to serve as theviscosity/dispersibility modifier include addition products of ethyleneoxide and, optionally, propylene oxide, with fatty alcohols, fattyacids, fatty amines, etc. They are referred to herein as ethoxylatedfatty alcohols, ethoxylated fatty acids, and ethoxylated fatty amines.

[0113] Any of the alkoxylated materials of the particular type describedhereinafter can be used as the nonionic surfactant. In general terms,the nonionics herein, when used alone, in liquid compositions are at alevel of from 0% to 5%, preferably from 0.1% to 5%, more preferably from0.2% to 3%. Suitable compounds are substantially water-solublesurfactants of the general formula:

R²—Y—(C₂H₄O)_(Z)—C₂H₄OH

[0114] wherein R² for both solid and liquid compositions is selectedfrom the group consisting of primary, secondary and branched chain alkyland/or acyl hydrocarbyl groups; primary, secondary and branched chainalkenyl hydrocarbyl groups; and primary, secondary and branched chainalkyl- and alkenyl-substituted phenolic hydrocarbyl groups; saidhydrocarbyl groups having a hydrocarbyl chain length of from 8 to 20,preferably from 10 to 18 carbon atoms. More preferably the hydrocarbylchain length for liquid compositions is from 16 to 18 carbon atoms andfor solid compositions from 10 to 14 carbon atoms. In the generalformula for the ethoxylated nonionic surfactants herein, Y is typically—O—, —C(O)O—, —C(O)N(R)—, or —C(O)N(R)R—, preferably —O—, and in whichR², and R, when present, have the meanings given hereinbefore, and/or Rcan be hydrogen, and z is at least 8, preferably at least 10-11.Performance and, usually, stability of the softener composition decreasewhen fewer ethoxylate groups are present.

[0115] The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to15. Of course, by defining R² and the number of ethoxylate groups, theHLB of the surfactant is, in general, determined. However, it is to benoted that the nonionic ethoxylated surfactants useful herein, forconcentrated liquid compositions, contain relatively long chain R²groups and are relatively highly ethoxylated. While shorter alkyl chainsurfactants having short ethoxylated groups can possess the requisiteHLB, they are not as effective herein.

[0116] Nonionic surfactants as the viscosity/dispersibility modifiersare preferred over the other modifiers disclosed herein for compositionswith higher levels of perfume.

[0117] Examples of nonionic surfactants follow. The nonionic surfactantsof this invention are not limited to these examples. In the examples,the integer defines the number of ethoxy (EO) groups in the molecule.

[0118] (3) Amine Oxides

[0119] Suitable amine oxides include those with one alkyl orhydroxyalkyl moiety of 8 to 22 carbon atoms, preferably from 10 to 18carbon atoms, more preferably from 8 to 14 carbon atoms, and two alkylmoieties selected from the group consisting of alkyl groups andhydroxyalkyl groups with 1 to 3 carbon atoms.

[0120] Examples include dimethyloctylamine oxide, diethyldecylamineoxide, bis-2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamineoxide, dipropyl-tetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.

[0121] (E) Stabilizers

[0122] Stabilizers can be present in the compositions of the presentinvention. The term “stabilizer,” as used herein, includes antioxidantsand reductive agents. These agents are present at a level of from 0% to2%, preferably from 0.01% to 0.2%, more preferably from 0.035% to 0.1%for antioxidants, and more preferably from 0.01% to 0.2% for reductiveagents. These assure good odor stability under long term storageconditions. Antioxidants and reductive agent stabilizers are especiallycritical for unscented or low scent products (no or low perfume).

[0123] Examples of antioxidants that can be added to the compositions ofthis invention include a mixture of ascorbic acid, ascorbic palmitate,propyl gallate, available from Eastman Chemical Products, Inc., underthe trade names Tenox® PG and Tenox® S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox®-6; butylated hydroxytoluene, available from UOPProcess Division under the trade name Sustane® BHT; tertiarybutylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;natural tocopherols, Eastman Chemical Products, Inc., as Tenox®GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,Inc., as BHA; long chain esters (C₈-C₂₂) of gallic acid, e.g., dodecylgallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171; Irganox® 1425;Irganox® 3114; Irganox® 3125; and mixtures thereof; preferablyIrganox®3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; morepreferably Irganox® 3125 alone or mixed with citric acid and/or otherchelators such as isopropyl citrate, Dequest® 2010, available fromMonsanto with a chemical name of 1-hydroxyethylidene-1,1-diphosphonicacid (etidronic acid), and Tiron®, available from Kodak with a chemicalname of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid.

[0124] (F) Soil Release Agent

[0125] In the present invention, an optional soil release agent can beadded. The addition of the soil release agent can occur in combinationwith the premix, in combination with the acid/water seat, before orafter electrolyte addition, or after the final composition is made. Thesoftening composition prepared by the process of the present inventionherein can contain from 0% to 10%, preferably from 0.2% to 5%, of a soilrelease agent. Preferably, such a soil release agent is a polymer.Polymeric soil release agents useful in the present invention includecopolymeric blocks of terephthalate and polyethylene oxide orpolypropylene oxide, and the like.

[0126] A preferred soil release agent is a copolymer having blocks ofterephthalate and polyethylene oxide. More specifically, these polymersare comprised of repeating units of ethylene terephthalate andpolyethylene oxide terephthalate at a molar ratio of ethyleneterephthalate units to polyethylene oxide terephthalate units of from25:75 to 35:65, said polyethylene oxide terephthalate containingpolyethylene oxide blocks having molecular weights of from 300 to 2000.The molecular weight of this polymeric soil release agent is in therange of from 5,000 to 55,000.

[0127] Another preferred polymeric soil release agent is acrystallizable polyester with repeat units of ethylene terephthalateunits containing from 10% to 15% by weight of ethylene terephthalateunits together with from 10% to 50% by weight of polyoxyethyleneterephthalate units, derived from a polyoxyethylene glycol of averagemolecular weight of from 300 to 6,000, and the molar ratio of ethyleneterephthalate units to polyoxyethylene terephthalate units in thecrystallizable polymeric compound is between 2:1 and 6:1. Examples ofthis polymer include the commercially available materials Zelcon 4780®(from Dupont) and Milease T® (from ICI).

[0128] Highly preferred soil release agents are polymers of the genericformula:

[0129] in which each X can be a suitable capping group, with each Xtypically being selected from the group consisting of H, and alkyl oracyl groups containing from 1 to 4 carbon atoms. p is selected for watersolubility and generally is from 6 to 113, preferably from 20 to 50. uis critical to formulation in a liquid composition having a relativelyhigh ionic strength. There should be very little material in which u isgreater than 10. Furthermore, there should be at least 20%, preferablyat least 40%, of material in which u ranges from 3 to 5.

[0130] The R¹⁴ moieties are essentially 1,4-phenylene moieties. As usedherein, the term “the R¹⁴ moieties are essentially 1,4-phenylenemoieties” refers to compounds where the R¹⁴ moieties consist entirely of1,4-phenylene moieties, or are partially substituted with other aryleneor alkarylene moieties, alkylene moieties, alkenylene moieties, ormixtures thereof. Arylene and alkarylene moieties which can be partiallysubstituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene,1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, andmixtures thereof. Alkylene and alkenylene moieties which can bepartially substituted include 1,2-propylene, 1,4-butylene,1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene,1,4-cyclohexylene, and mixtures thereof.

[0131] For the R¹⁴ moieties, the degree of partial substitution withmoieties other than 1,4-phenylene should be such that the soil releaseproperties of the compound are not adversely affected to any greatextent. Generally the degree of partial substitution which can betolerated will depend upon the backbone length of the compound, i.e.,longer backbones can have greater partial substitution for 1,4-phenylenemoieties. Usually, compounds where the R¹⁴ comprise from 50% to 100%1,4-phenylene moieties (from 0% to 50% moieties other than1,4-phenylene) have adequate soil release activity. For example,polyesters made according to the present invention with a 40:60 moleratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene)acid have adequate soil release activity. However, because mostpolyesters used in fiber making comprise ethylene terephthalate units,it is usually desirable to minimize the degree of partial substitutionwith moieties other than 1,4-phenylene for best soil release activity.Preferably, the R¹⁴moieties consist entirely of (i.e., comprise 100%)1,4-phenylene moieties, i.e., each R¹⁴ moiety is 1,4-phenylene.

[0132] For the R¹⁵ moieties, suitable ethylene or substituted ethylenemoieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene,3-methoxy-1,2-propylene, and mixtures thereof. Preferably, the R¹⁵moieties are essentially ethylene moieties, 1,2-propylene moieties, ormixtures thereof. Inclusion of a greater percentage of ethylene moietiestends to improve the soil release activity of compounds. Surprisingly,inclusion of a greater percentage of 1,2-propylene moieties tends toimprove the water solubility of compounds.

[0133] Therefore, the use of 1,2-propylene moieties or a similarbranched equivalent is desirable for incorporation of any substantialpart of the soil release component in the liquid fabric softenercompositions. Preferably, from 75% to 100%, are 1,2-propylene moieties.

[0134] The value for each p is at least 6, and preferably is at least10. The value for each n usually ranges from 12 to 113. Typically thevalue for each p is in the range of from 12 to 43.

[0135] A more complete disclosure of soil release agents is contained inU.S. Pat. Nos.: 4,661,267; 4,711,730; 4,749,596; 4,818,569; 4,877,896;4,956,447; and 4,976,879, all of said patents being incorporated hereinby reference.

[0136] These soil release agents can also act as scum dispersants.

[0137] (G) Scum Dispersant

[0138] In the present invention, the premix can be combined with anoptional scum dispersant, other than the soil release agent, and heatedto a temperature at or above the melting point(s) of the components.

[0139] The preferred scum dispersants herein are formed by highlyethoxylating hydrophobic materials. The hydrophobic material can be afatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide,quaternary ammonium compound, or the hydrophobic moieties used to formsoil release polymers. The preferred scum dispersants are highlyethoxylated, e.g., more than 17, preferably more than 25, morepreferably more than 40, moles of ethylene oxide per molecule on theaverage, with the polyethylene oxide portion being from 76% to 97%,preferably from 81% to 94%, of the total molecular weight.

[0140] The level of scum dispersant is sufficient to keep the scum at anacceptable, preferably unnoticeable to the consumer, level under theconditions of use, but not enough to adversely affect softening. Forsome purposes it is desirable that the scum is nonexistent. Depending onthe amount of anionic or nonionic detergent, etc., used in the washcycle of a typical laundering process, the efficiency of the rinsingsteps prior to the introduction of the compositions herein, and thewater hardness, the amount of anionic or nonionic detergent surfactantand detergency builder (especially phosphates and zeolites) entrapped inthe fabric (laundry) will vary. Normally, the minimum amount of scumdispersant should be used to avoid adversely affecting softeningproperties. Typically scum dispersion requires at least 2%, preferablyat least 4% (at least 6% and preferably at least 10% for maximum scumavoidance) based upon the level of softener active. However, at levelsof 10% (relative to the softener material) or more, one risks loss ofsoftening efficacy of the product especially when the fabrics containhigh proportions of nonionic surfactant which has been absorbed duringthe washing operation.

[0141] Preferred scum dispersants are: Brij 700®; Varonic U-250®;Genapol T-500®) Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.

[0142] (H) Bactericides

[0143] Examples of bactericides used in the compositions of thisinvention include glutaraldehyde, formaldehyde,2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located inPhiladelphia, Pa., under the trade name Bronopol®, and a mixture of5-chloro-2-methyl-4-isothiazoline-3-one and2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under thetrade name Kathon 1 to 1,000 ppm by weight of the agent.

[0144] (I) Perfume

[0145] The present invention can contain any softener compatibleperfume. Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138,said patent being incorporated herein by reference.

[0146] As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

[0147] Examples of perfume ingredients useful in the perfumes of thepresent invention compositions include, but are not limited to, hexylcinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexylsalicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol;3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol;3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

[0148] Additional examples of fragrance materials include, but are notlimited to, orange oil; lemon oil; grapefruit oil; bergamot oil; cloveoil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiff's base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-hydroxy-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol;5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of: hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

[0149] More examples of perfume components are geraniol; geranylacetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol;citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate;tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate;2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate;benzyl salicylate; benzyl benzoate; styrallyl acetate;dimethylbenzylcarbinol; trichloromethylphenylcarbinylmethylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate;vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionomes; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

[0150] The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

[0151] Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

[0152] Perfume can be present at a level of from 0% to 10%, preferablyfrom 0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric softener compositions of the presentinvention provide improved fabric perfume deposition.

[0153] (J) Chelating Agents

[0154] The compositions and processes herein can optionally employ oneor more copper and/or nickel chelating agents (“chelators”). Suchwater-soluble chelating agents can be selected from the group consistingof amino carboxylates, amino phosphonates, polyfunctionally-substitutedaromatic chelating agents and mixtures thereof, all as hereinafterdefined. The whiteness and/or brightness of fabrics are substantiallyimproved or restored by such chelating agents and the stability of thematerials in the compositions are improved.

[0155] Amino carboxylates useful as chelating agents herein includeethylenedi-aminetetraacetates (EDTA),N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA),ethylenediamine tetraproprionates, ethylenediamine-N,N′-diglutamates,2-hyroxypropylenediamine-N,N′-disuccinates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates(DETPA), and ethanoldiglycines, including their water-soluble salts suchas the alkali metal, ammonium, and substituted ammonium salts thereofand mixtures thereof.

[0156] Amino phosphonates are also suitable for use as chelating agentsin the compositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates),diethylenetriamine-N,N,N′,N″,N″-pentakis(methane phosphonate) (DETMP)and 1-hydroxyethane-1,1-diphosphonate (HEDP). Preferably, these aminophosphonates to not contain alkyl or alkenyl groups with more than 6carbon atoms.

[0157] The chelating agents are typically used in the present rinseprocess at levels from 2 ppm to 25 ppm, for periods from 1 minute up toseveral hours' soaking.

[0158] The preferred EDDS chelator used herein (also known asethylenediamine-N,N′-disuccinate) is the material described in U.S. Pat.No. 4,704,233, cited hereinabove, and has the formula (shown in freeacid form):

[0159] As disclosed in the patent, EDDS can be prepared using maleicanhydride and ethylenediamine. The preferred biodegradable [S,S] isomerof EDDS can be prepared by reacting L-aspartic acid with1,2-dibromoethane. The EDDS has advantages over other chelators in thatit is effective for chelating both copper and nickel cations, isavailable in a biodegradable form, and does not contain phosphorus. TheEDDS employed herein as a chelator is typically in its salt form, i.e.,wherein one or more of the four acidic hydrogens are replaced by awater-soluble cation M, such as sodium, potassium, ammonium,triethanolammonium, and the like. As noted before, the EDDS chelator isalso typically used in the present rinse process at levels from 2 ppm to25 ppm for periods from 1 minute up to several hours' soaking. Atcertain pH's the EDDS is preferably used in combination with zinccations.

[0160] As can be seen from the foregoing, a wide variety of chelatorscan be used herein. Indeed, simple polycarboxylates such as citrate,oxydisuccinate, and the like, can also be used, although such chelatorsare not as effective as the amino carboxylates and phosphonates, on aweight basis. Accordingly, usage levels may be adjusted to take intoaccount differing degrees of chelating effectiveness. The chelatorsherein will preferably have a stability constant (of the fully ionizedchelator) for copper ions of at least 5, preferably at least 7.Typically, the chelators will comprise from 0.5% to 10%, more preferablyfrom 0.75% to 5%, by weight of the compositions herein.

[0161] Preferred chelators include DETMP, DETPA, NTA, EDDS and mixturesthereof.

[0162] (K)-Enzyme

[0163] The compositions and processes herein can optionally employ oneor more enzymes such as lipases, proteases, cellulase, amylases andperoxidases. A preferred enzyme for use herein is a cellulase enzyme.Indeed, this type of enzyme will further provide a color care benefit tothe treated fabric. Cellulases usable herein include both bacterial andfungal types, preferably having a pH optimum between 5 and 9.5. U.S.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96/34092, WO96/34945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.Stated otherwise, the compositions herein will typically comprise from0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzymepreparation. In the particular cases where activity of the enzymepreparation can be defined otherwise such as with cellulases,corresponding activity units are preferred (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from about 0.5 to 1000 CEVU/gram of composition. Cellulaseenzyme preparations used for the purpose of formulating the compositionsof this invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.

[0164] (L) Other Optional Ingredients

[0165] The present invention can include optional componentsconventionally used in textile treatment compositions, for example:colorants; preservatives; surfactants; anti-shrinkage agents; fabriccrisping agents; spotting agents; germicides; fungicides; anti-oxidantssuch as butylated hydroxy toluene, anti-corrosion agents, and the like.

[0166] The present invention can also include other compatibleingredients, including those as disclosed in copending applications Ser.No. 081372,068, filed Jan. 12, 1995, Rusche, et al.; Ser. No.08/372,490, filed Jan. 12, 1995, Shaw, et al.; and Ser. No. 08/277,558,filed Jul. 19, 1994, Hartman, et al., incorporated herein by reference.

[0167] Fabric Softener Processing

[0168] Also within the scope of the present invention, is a process forpreparing a premix composition and a fabric softener composition fromthe premix. According to another aspect of the invention, the premixcomposition comprises a fabric softener compound of the invention and aneffective amount of a component selected from the group consisting ofprincipal solvents, low molecular weight water soluble solvents, watersoluble calcium salt, water soluble magnesium salt, perfume, andmixtures thereof.

[0169] The use of a principal solvent allows the preparation of premixescomprising the softener active (from 55% to 85%, preferably from 60% to80%, more preferably from 65% to 75%, by weight of the premix); theprincipal solvent (from 10% to 30%, preferably from 13% to 25%, morepreferably from 15% to 20%, by weight of the premix); and optionally,the water soluble solvent (from 5% to 20%, preferably from 5% to 17%,more preferably from 5% to 15%, by weight of the premix). These premixescontain the desired amount of fabric softening active and sufficientprincipal solvent and, optionally, solvent to give the premix thedesired viscosity for the desired temperature range. Typical viscositiessuitable for processing are less than 1000 cps, preferably less than 500cps, more preferably less than 300 cps. Use of low temperatures improvessafety, by minimizing solvent vaporization, minimizes the degradationand/or loss of materials such as the biodegradable fabric softeneractive, perfumes, etc., and reduces the need for heating, thus saving onthe expenses for processing. The result is improved environmental impactand safety from the manufacturing operation.

[0170] Examples of premixes and processes using them include premixeswhich typically contain from 55% to 85%, preferably from 60% to 80%,more preferably from 65% to 75%, of fabric softener active asexemplified in the Examples, mixed with from 10% to 30%, preferably from13% to 25%, more preferably from 15% to 20%, of principal solvent suchas 1,2-hexanediol, and from 5% to 20%, preferably from 5% to 15%, ofwater soluble solvent like ethanol and/or isopropanol and/or hexyleneglycol.

[0171] These premixes can be used to formulate fabric softeningcompositions in processes comprising the steps of:

[0172] 1. Make premix of fabric softening active, 11% ethanol, and 17%principal solvent, let cool to ambient temperature.

[0173] 2. Mix perfume in the premix.

[0174] 3. Make up water seat of water and HCl at ambient temperature.Optionally add chelant and/or antioxidant.

[0175] 4. Add premix to water under good agitation.

[0176] 5. Trim with CaCl₂ solution to desired viscosity.

[0177] 6. Add dye solution to get desired color.

[0178] Typically, the pH of the premix in water is adjusted to from 1.5to 5. The diester quaternary fabric softening actives (DEQAs); theprincipal solvents and, optionally, the water soluble solvents, can beformulated as premixes which can be used to prepare fabric softeningcompositions.

Solid Compositions

[0179] 1. Solid particulate compositions

[0180] As discussed hereinbefore, the invention also comprises solidparticulate composition comprising:

[0181] (A) from 50% to 95%, preferably from 60% to 90%, of saidbiodegradable fabric softening active;

[0182] (B) optionally, from 0% to 30%, preferably from 3% to 15%, ofdispersibility modifier; and

[0183] (D) from 0% to 10% of a pH modifier.

[0184] Optional pH Modifier

[0185] Since the biodegradable ester fabric softener actives aresomewhat labile to hydrolysis, it is preferable to include optional pHmodifiers in the solid particulate composition to which water is to beadded, to form stable dilute or concentrated liquid softenercompositions. Said stable liquid compositions should have a pH (neat) offrom 2 to 5, preferably from 2 to 4.5, more preferably from 2 to 4, andmost preferably from 3 to 4.

[0186] The pH can be adjusted by incorporating a solid, water solubleBronsted acid. Examples of suitable Bronsted acids include inorganicmineral acids, such as boric acid, sodium bisulfate, potassiumbisulfate, sodium phosphate monobasic, potassium phosphate monobasic,and mixtures thereof; organic acids, such as citric acid, fumaric acid,maleic acid, malic acid, tannic acid, gluconic acid, glutamic acid,tartaric acid, glycolic acid, chloroacetic acid, phenoxyacetic acid,1,2,3,4-butane tetracarboxylic acid, benzene sulfonic acid, benzenephosphonic acid, ortho-toluene sulfonic acid, para-toluene sulfonicacid, phenol sulfonic acid, naphthalene sulfonic acid, oxalic acid,1,2,4,5-pyromellitic acid, 1,2,4-trimellitic acid, adipic acid, benzoicacid, phenylacetic acid, salicylic acid, succinic acid, and mixturesthereof; and mixtures of mineral inorganic acids and organic acids.Preferred pH modifiers are citric acid, gluconic acid, tartaric acid,1,2,3,4-butane tetracarboxylic acid, malic acid, and mixtures thereof.

[0187] Optionally, materials that can form solid clathrates such ascyclodextrins and/or zeolites, etc., can be used as adjuvants in thesolid particulate composition as host carriers of concentrated liquidacids and/or anhydrides, such as acetic acid, HCl, sulfuric acid,phosphoric acid, nitric acid, carbonic acid, etc. An example of suchsolid clatherates is carbon dioxide adsorbed in zeolite A, as disclosedin U.S. Pat. No. 3,888,998 and U.S. Pat. No. 4,007,134 both of saidpatents being incorporated herein by reference. Examples of inclusioncomplexes of phosphoric acid, sulfuric acid, and nitric acid, andprocess for their preparation are disclosed in U.S. Pat. No. 4,365,061said patent being incorporated herein by reference.

[0188] When used, the pH modifier is typically used at a level of from0.01% to 10%, preferably from 0.1% to 5%, by weight of the composition.

[0189] Preparation of Solid Particulate Granular Fabric Softener

[0190] The granules can be formed by preparing a melt, solidifying it bycooling, and then grinding and sieving to the desired size. In athree-component mixture, e.g., nonionic surfactant, single-long-chaincationic, and DEQA, it is more preferred, when forming the granules, topre-mix the nonionic surfactant and the more soluble single-long-chainalkyl cationic compound before mixing in a melt of the diesterquaternary ammonium cationic compound.

[0191] It is highly preferred that the primary particles of the granuleshave a diameter of from 50 to 1,000, preferably from 50 to 400, morepreferably from 50 to 200, microns. The granules can comprise smallerand larger particles, but preferably from 85% to 95%, more preferablyfrom 95% to 100%, are within the indicated ranges. Smaller and largerparticles do not provide optimum emulsions/dispersions when added towater. Other methods of preparing the primary particles can be usedincluding spray cooling of the melt. The primary particles can beagglomerated to form a dust-free, non-tacky, free-flowing powder. Theagglomeration can take place in a conventional agglomeration unit (i.e.,Zig-Zag Blender, Lodige) by means of a water-soluble binder. Examples ofwater-soluble binders useful in the above agglomeration process includeglycerol, polyethylene glycols, polymers such as PVA, polyacrylates, andnatural polymers such as sugars.

[0192] The flowability of the granules can be improved by treating thesurface of the granules with flow improvers such as clay, silica orzeolite particles, water-soluble inorganic salts, starch, etc.

[0193] Method of Use

[0194] Water can be added to the particulate, solid, granularcompositions to form dilute or concentrated liquid softener compositionsfor later addition to the rinse cycle of the laundry process with aconcentration of said biodegradable cationic softening compound of from0.5% to 50%, preferably from 1% to 35%, more preferably from 4% to 32%by weight. The particulate, rinse-added solid composition (1) can alsobe used directly in the rinse bath to provide adequate usageconcentration (e.g., from 10 to 1,000 ppm, preferably from 50 to 500ppm, of total softener active ingredient). The liquid compositions canbe added to the rinse to provide the same usage concentrations.

[0195] The water temperature for preparation should be from 20° C. to90° C., preferably from 25° C. to 80° C. Single-long-chain alkylcationic surfactants as the viscosity/dispersibility modifier at a levelof from 0% to 15%, preferably from 3% to 15%, more preferably from 5% to15%, by weight of the composition, are preferred for the solidcomposition. Nonionic surfactants at a level of from 5% to 20%,preferably from 8% to 15%, as well as mixtures of these agents can alsoserve effectively as the viscosity/dispersibility modifier.

[0196] The emulsified/dispersed particles, formed when the said granulesare added to water to form aqueous concentrates, typically have anaverage particle size of less than 10 microns, preferably less than 2microns, and more preferably from 0.2 to 2 microns, in order thateffective deposition onto fabrics is achieved. The term “averageparticle size,” in the context of this specification, means a numberaverage particle size, i.e., more than 50% of the particles have adiameter less than the specified size.

[0197] Particle size for the emulsified/dispersed particles isdetermined using, e.g., a Malvern particle size analyzer.

[0198] Depending upon the particular selection of nonionic and cationicsurfactant, it may be desirable in certain cases, when using the solidsto prepare the liquid, to employ an efficient means for dispersing andemulsifying the particles (e.g., blender).

[0199] Solid particulate compositions used to make liquid compositionscan, optionally, contain electrolytes, perfume, antifoam agents, flowaids (e.g., silica), dye, preservatives, and/or other optionalingredients described hereinbefore.

[0200] The benefits of adding water to the particulate solid compositionto form aqueous compositions to be added later to the rinse bath includethe ability to transport less weight thereby making shipping moreeconomical, and the ability to form liquid compositions similar to thosethat are normally sold to consumers, e.g., those that are describedherein, with lower energy input (i.e., less shear and/or lowertemperature). Furthermore, the particulate granular solid fabricsoftener compositions, when sold directly to the consumers, have lesspackaging requirements and smaller, more disposable containers. Theconsumers will then add the compositions to available, more permanent,containers, and add water to pre-dilute the compositions, which are thenready for use in the rinse bath, just like the liquid compositionsherein. The liquid form is easier to handle, since it simplifiesmeasuring and dispensing.

[0201] 2. Dryer Activated Compositions

[0202] The present invention also relates to improved soliddryer-activated fabric softener compositions which are either (A)incorporated into articles of manufacture, e.g., on a substrate, or, are(B) in the form of particles similar to those disclosed above.(including, where appropriate, agglomerates, pellets, and tablets ofsaid particles). Such compositions typically contain from 10% to 95% offabric softening agent.

[0203] A. Substrate Articles

[0204] In preferred embodiments, the present invention encompassesarticles of manufacture. Representative articles are those that areadapted for use to provide unique perfume benefits and to soften fabricsin an automatic laundry dryer, of the types disclosed in U.S. Pat. Nos.:3,989,631; 4,055,248; 4,073,996; 4,022,938; 4,764,289; 4,808,086;4,103,047; 3,736,668; 3,701,202; 3,634,947; 3,633,538; and 3,435,537;and 4,000,340,, all of said patents being incorporated herein byreference.

[0205] Typical articles of manufacture of this type include articlescomprising:

[0206] I. a fabric conditioning composition comprising from 30% to 95%of normally solid, dryer softenable fabric softening agent comprisingsaid biodegradable fabric softening active; and

[0207] II. a dispensing means which provides for release of an effectiveamount of said composition including an effective amount of ii,sufficient to provide odor control, to fabrics in an automatic laundrydryer at automatic laundry dryer operating temperatures, e.g., from 35°C. to 115° C.

[0208] When the dispensing means is a flexible substrate, e.g., in sheetconfiguration, the fabric conditioning composition is releasably affixedon the substrate to provide a weight ratio of conditioning compositionto dry substrate ranging from 10:1 to 0.5:1, preferably from 5:1 to 1:1.

[0209] The solid fabric softener compositions herein can includecationic and nonionic fabric softener actives used in combination witheach other.

EXAMPLES

[0210] The synthesis of the fabric softening compound of the presentinvention is further illustrated in the following Synthesis Examples.These Synthesis Examples are provided for purposes of illustration only.

Fatty Acid Compound Synthesis Example A

[0211] 1,300 grams of food grade (refined, bleached, degummed) canolaoil and approximately 6.5 grams of a commercial nickel hydrogenationcatalyst (Engelhard, “N-545”®) corresponding to approximately 0.13 wt. %Ni, are placed in a hydrogenation reactor which is equipped withstirrer. The reactor is sealed and evacuated. The contents are heated to170° C. and hydrogen is fed into the reactor. Stirring at 450 rpm ismaintained throughout the reaction. After 10 minutes the temperature inthe reactor is 191° C. and the hydrogen pressure is 11 psig. Thetemperature is held at 190° C. After 127 minutes from when the hydrogenfeed began, the hydrogen pressure is 10 psig. A sample of the reactionmass is drawn and found to have an iodine Value of 78.0 and a cis:transratio of 1.098. After another 20 minutes at 190° C., the hydrogenpressure is 9.8 psig. The hydrogen feed is discontinued and the reactorcontents cooled with stirring. The final reaction product has an IodineValue of 74.5 and a cis:trans ratio of 1.35.

[0212] The product that forms in the reactor is removed and filtered. Ithas a cloud point of 22.2° C. The chain length distributions of the acylsubstituents on the sample taken at 127 minutes, and of the finalproduct, are determined to be as shown in Table 1 in which “sat.” meanssaturated, and “mono” and “di” means monounsaturated and diunsaturated,respectively. TABLE 1 Approximate Percent (mol.) Chain length Sample @127 min. Product C14-sat. 0.1 0.1 C16-sat. 4.7 4.6 C16-mono. 0.4 0.4C18-sat. 8.9 13.25 C18-mono. 77.0  73.8  C18-di. 4.5 3.1 C20-sat. 0.70.75 C-20-mono. 2.1 2.0 Other 1.6 2.0

Fatty Acid Compound Synthesis Example B

[0213] 1,300 grams of food grade canola oil and 5.2 grams of Engelhard“N-545” ® nickel hydrogenation catalyst are placed in a hydrogenationreactor which is equipped with a stirrer. The reactor is sealed andevacuated. The contents are heated to 175° C. and hydrogen is fed intothe reactor. Stirring is maintained at 450 rpm throughout the course ofreaction. After 5 minutes the temperature in the reactor is 190° C. andthe hydrogen pressure is 7 psig.

[0214] The temperature is held at 190° C. After 125 minutes from thestart of the hydrogen feed, the hydrogen pressure is 7 psig. A sample ofthe reaction mass is drawn and found to have an Iodine Value of 85.4.After another 20 minutes at 190° C., the hydrogen pressure is 6 psig.The hydrogen feed is discontinued and the reactor contents cooled withstirring. The final reaction product has an Iodine Value of 80.0. Theproduct that forms in the reactor is removed and filtered. It has acloud point of 18.6° C.

Fatty Acid Compound Synthesis Example C

[0215] 1,300 grams of food grade canola oil and 2.9 grams of Engelhard“N-545” nickel hydrogenation catalyst are placed in a hydrogenationreactor which is equipped with a stirrer. The reactor is sealed andevacuated. The contents are heated to 180° C. and hydrogen is fed intothe reactor. Stirring is maintained at 450 rpm throughout the course ofthe reaction. After 5minutes the temperature in the reactor is 192° C.and the hydrogen pressure is 10 psig. The temperature is held at 190±3°C. After 105 minutes from the start of the hydrogen feed, the hydrogenpressure is 10 psig. A sample of the reaction mass is drawn and found tohave an Iodine Value of 85.5. After another 20 minutes at 190° C., thehydrogen pressure is 10 psig. The hydrogen feed is discontinued and thereactor contents cooled with stirring. The final reaction product has anIodine Value of 82.4. The product that forms in the reactor is removedand filtered. It has a cloud point of 17.2” C.

Fatty Acid Compound Synthesis Example D

[0216] 1,300 grams of food grade canola oil and 1.4 grams of Engelhard“N-545”® nickel hydrogenation catalyst are placed in a hydrogenationreactor which is equipped with a stirrer. The reactor is sealed andevacuated. The contents are heated to 180° C. and hydrogen is fed intothe reactor. After 5 minutes the temperature in the reactor is 191° C.and the hydrogen pressure is 10 psig. The temperature is held at 190±3°C. After 100 minutes from the start of the hydrogen feed, the hydrogenpressure is 10 psig. A sample of the reaction mass is drawn and found tohave an Iodine Value of 95.4. After another 20 minutes at 190° C., thehydrogen pressure is 10 psig. The hydrogen feed is discontinued and thereactor contents cooled with stirring. The final reaction product had anIodine Value of 2.3. The product that forms in the reactor is removedand filtered. It has a cloud point of 34° C.

Fatty Acid Compound Synthesis Example E

[0217] 1,300 grams of food grade canola oil and 1.3 grams of Engelhard“N-545” ® nickel hydrogenation catalyst are placed in a hydrogenationreactor which is equipped with a stirrer. The reactor is sealed andevacuated. The contents are heated to 190° C. and hydrogen is fed intothe reactor to a hydrogen pressure of 5 psig. After 3 hours from thestart of the hydrogen feed, a sample of the reaction mass is drawn andfound to have an iodine value of 98. The hydrogenation is interrupted,another 0.7 grams of the same catalyst is added, and the reactionconditions are reestablished at 190° C. for another 1 hour. The hydrogenfeed is then discontinued and the reactor contents cooled with stirring.The final reaction product had an Iodine Value of 89.9. The product thatforms in the reactor is removed and filtered. It has a cloud point of16.0° C.

Fatty Acid Compound Synthesis Example F

[0218] 1,300 grams of food grade canola oil and 2.0 grams of Engelhard“N-545” ® nickel hydrogenation catalyst are placed in a hydrogenationreactor which is equipped with a stirrer. The reactor is sealed andevacuated. The contents are heated to 190° C. and hydrogen is fed intothe reactor to a hydrogen pressure of 5 psig. Stirring is maintained at420 rpm throughout the course of reaction of the hydrogen feed. After130 minutes from the start of the hydrogen feed, the hydrogen feed isdiscontinued and the reactor contents cooled with stirring. The finalreaction product had an Iodine Value of 96.4. The product that forms inthe reactor is removed and filtered. It has a cloud point of 11.2° C.

Fatty acid Compound Synthesis Example G

[0219] A mixture of 1,200 grams of the hydrogenated oil from SynthesisExample F and 200 grams of the hydrogenated oil from Synthesis Example Ais hydrolyzed three times with 250° C. steam at 600 psig for 2.5 hoursat a ratio of steam:oil of 1.2 (by weight). An aqueous solutioncontaining the glycerine which had split off is removed.

[0220] The resulting mixture of fatty acids is vacuum distilled for atotal of 150 minutes, in which the pot temperature rose gradually from200° C. to 238° C. and the head temperature rose gradually from 175° C.to 197° C. Vacuum of 0.3-0.6 mm is maintained.

[0221] The fatty acids product of the vacuum distillation has an IodineValue of 99.1, an amine value (AV) of 197.6 and a saponification value(SAP) of 198.6.

[0222] The following are synthesis examples of softener compoundsaacording to the present invention:

Synthesis Example of Softener Compound 1

[0223] 1)-Esterification:

[0224] 489 grams of partly hydrogenated tallow fatty acid with an IV of45 and an Acid Value of 206, commercially available under the tradenameDistal 51 and sold by Witco Corporation, is added into the reactor, thereactor is flushed with N2 and 149 grams of triethanolamine is addedunder agitation. The molar ratio of fatty acid to triethanol amine is of1.8:1. The mixture is heated above 150 C and the pressure is reduced toremove the water of condensation. The reaction is prolonged until anAcid Value of 5 is reached.

[0225] The above mentioned partly hydrogenated tallow fatty acid is alsocommercially available from Henkel under the tradename Edenor HtiCT, orcommercially available from Unichema under the tradename Prifac 5905.

[0226] 2)-Quaternization:

[0227] To 627 grams of the product of condensation, 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50° C. and the reaction is followed by verifyingthe residual amine value. 749 grams of softener compound of theinvention is obtained.

[0228] The quaternized material is optionally diluted with e.g. 15% ofisopropanol which lower the melting point of the material therebyproviding a better ease in the handling of the material.

Synthesis Example of Softener Compound 2

[0229] 1)-Esterification:

[0230] 504 grams of oleic fatty acid with an IV of 90 and an Acid Valueof 198, commercially available under the tradename Emersol 233 and soldby Henkel Corporation, is added into the reactor, the reactor is flushedwith N2 and 149 grams of triethanolamine is added under agitation. Themolar ratio of fatty acid to triethanol amine is of 1.8:1. The mixtureis heated above 150 C and the pressure is reduced to remove the water ofcondensation. The reaction is prolonged until an Acid Value of 2 isreached.

[0231] The above mentioned oleic fatty acid is also commerciallyavailable from Henkel under the tradename Edenor TiO5.

[0232] 2)-Quaternization:

[0233] To the 629 grams of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

[0234] 751 grams of softener compound of the invention is obtained.

[0235] The quaternized material is optionally diluted with e.g. 8% ofethanol which lower the melting point of the material thereby providinga better ease in the handling of the material.

Synthesis Example of softener compound 3

[0236] 1-Esterification:

[0237] 571 grams of Canola fatty acid with an IV of about 100 and anAcid Value of about 196 as made according to Fatty Acid CompoundSynthesis Example G is added into the reactor, the reactor is flushedwith N2 and 149 grams of triethanolamine is added under agitation. Themolar ratio of fatty acid to triethanol amine is of 2.0:1. The mixtureis heated above 150 C and the pressure is reduced to remove the water ofcondensation. The reaction is prolonged until an Acid Value of 3 isreached.

[0238] 2)-Quaternization:

[0239] To the 698 grammes of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

[0240] 820 grams of softener compound of the invention is obtained.

[0241] The quaternized material is optionally diluted with e.g. 15% of a50:50 ethanol/hexyleneglycol mixture which lower the melting point ofthe material thereby providing a better ease in the handling of thematerial.

Synthesis Example of Softener Compound 4

[0242] 1)-Esterification:

[0243] 457 grams of Canola fatty acid with an IV of about 100 and anAcid Value of about 196, as made according to Fatty Acid CompoundSynthesis Example G, is added into the reactor, the reactor is flushedwith N2 and 149 grams of triethanolamine is added under agitation. Themolar ratio of fatty acid to triethanol amine is of 1.6:1. The mixtureis heated above 150 C and the pressure is reduced to remove the water ofcondensation. The reaction is prolonged until an Acid Value of 1 isreached.

[0244] 2)-Quaternization:

[0245] To the 582 grams of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

[0246] 704 grams of softener compound of the invention is obtained.

[0247] The quaternized material is optionally diluted with e.g. 8% ofethanol which lower the melting point of the material thereby providinga better ease in the handling of the material.

[0248] The above synthesised softener compound are also exemplifiedbelow in the non-limiting fabric softening composition examples.

[0249] Abbreviations used in the Examples

[0250] In the softening compositions, the abreviated componentidentification have the following meanings:

[0251] Softener compound 1: Softener compound as made according toSynthesis Example of softener compound 1

[0252] Softener compound 2: Softener compound as made according toSynthesis Example of softener compound 2

[0253] Softener compound 3: Softener compound as made according toSynthesis Example of softener compound 3

[0254] Softener compound 4: Softener compound as made according toSynthesis Example of softener compound 4

[0255] IPA: Isopropylalcohol

[0256] TMPD: 2,2,4-trimethyl-1,3-pentanediol

[0257] CHDM: 1,4 cyclohexanedimethanol 1 2 3 4 5 Softener 8.0 — — — —compound 1 Softener — 8.0 20 30 28 compound 2 IPA 1.4 — — — — Ethanol —0.7 1.7 2.6 2.4 1,2 Hexanediol — 10 15 — — 2-ethyl-1,3- — — — — 12hexanediol TMPD — — — 12 — CHDM — — — 5 5 HCl 0.02 0.02 0.02 0.02 0.02Calcium 0.04 — — — — chloride Perfume 0.5 0.5 1.0 2.0 2.0 Dye 5 ppm 5ppm 5 ppm 5 ppm 5 ppm Deminerised Balance Balance Balance BalanceBalance water 6 7 8 9 Softener 8.0 25 — 28 compound 3 Softener — — 30 —compound 4 Ethanol 0.7 2.2 2.6 2.5 Hexylene glycol 0.7 2.2 — 2.5 1,2Hexanediol 9 12 15 5 TMPD — 5 — 9 HCl 0.02 0.02 0.02 0.02 Perfume 0.51.5 1.0 2.0 Dye 5 ppm 20 ppm 20 ppm 5 ppm Demin water Balance BalanceBalance Balance

What is claimed is: 1- A biodegradable fabric softener compoundcomprising a quaternary ammonium salt, the quaternised ammonium saltbeing a quaternised product product of condensation between: a)-afraction of saturated or unsaturated, linear or branched fatty acids, orof derivatives of said acids, said fatty acids or derivatives eachpossessing a hydrocarbon chain in which the number of atoms is between 5and 21, and b)-triethanolamine, characterised in that said condensationproduct has an acid value, measured by titration of the condensationproduct with a standard KOH solution against a phenolphtaleineindicator, of less than 6.5. 2- Biodegradable fabric softener compoundaccording to claim 1, wherein the fatty acid fraction contains cis andtrans isomers with a cis/trans ratio of from 1:1 to 50:1, preferably offrom 3:1 to 50:1, and more preferably from 4:1 to 20:1. 3- Biodegradablefabric softener compound according to either one of claim 1 or 2,wherein the fatty acid/triethanolamine mole ratio is from 1:1 to 2.5:1.4- Biodegradable fabric softener compound according to any one of claim1-3, wherein the fatty acid/triethanolamine mole ratio is from 1.4:1 to1.8:1, preferably 1.5:1. 5- Biodegradable fabric softener compoundaccording to any one of claim 1-3, wherein the fattyacid/triethanolamine mole ratio is from 1.8:1 to 2.2:1, preferably2.0:1. 6- Biodegradable fabric softener compound according to any one ofclaim 1-5, wherein said compound has an acid value of less than 5,preferably less than
 3. 7- Biodegradable fabric softener compoundaccording to any one of claim 1-6, wherein said compound has theformula: [(R)_(4-m)—N⁽⁺⁾—[(CH₂)_(n)—Y—R¹]_(m)]X⁽⁻⁾  (1) wherein each Rsubstituent is hydrogen or a short chain C₁-C₆ alkyl or hydroxyalkylgroup; each m is 2 or 3; each n is from 1 to 4; each Y is —O—(O)C—,—(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—; the sum of carbons in each R¹,plus one when Y is —O—(O)C— or —(R)N—(O)C—, is C₆-C₂₂, but no more thanone R¹, or YR¹, sum being less than 12 and then the other R¹, or YR¹,sum is at least 16, with each R¹ comprising a long chain C₅-C₂₁ branchedalkyl or unsaturated alkyl, optionally substituted, the ratio ofbranched alkyl to unsaturated alkyl being from 5:95 to 95:5, and for theunsaturated alkyl group, the Iodine Value of the parent fatty acid ofthis R¹ group is from 20 to 140, and wherein the counterion, X⁻ is asoftener-compatible anion. 8- Biodegradable fabric softener compoundaccording to claim 7, wherein the softener compound contains up to 20%of mono-long chain softener in which one YR¹ group is —OH, —N(R)H, or—C(O)OH. 9- A fabric softening composition comprising a biodegradablefabric softener compound as defined in any one of claims 1-8, whereinsaid biodegradable fabric softener active is present in an amount offrom 1% to 80%, by weight of the composition. 10- A fabric softeningcomposition according to claim 9, wherein said composition comprisesless than 40%, by weight of the composition of a principal solventhaving a ClogP of from 0.15 to 0.64. 11- A fabric softening compositionaccording to claim 10, wherein said principal solvent is selected frommono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols, and mixtures thereof. 12- A fabric softeningcomposition according to either one of claim 10 or 11, wherein theprincipal solvent is selected from 2,2,4-trimethyl-1,3-pentanediol,ethoxylates of 2,2,4-trimethyl-1,3-pentanediol, 1,2 hexanediol,ethoxylates of 2-ethyl-1,3-hexanediol, 1,2 cyclohexanedimethanol, andmixtures thereof. 13- A fabric softening composition according to claim12, wherein said principal solvent is present in a combination form of2,2,4-trimethyl-1,3-pentanediol and 1,2 hexanediol 14- A fabricsoftening composition according to any one of claim 10-13, wherein saidcomposition comprises an effective amount, sufficient to improveclarity, of low molecular weight water soluble solvents selected fromthe group consisting of: ethanol, isopropanol, propylene glycol,1,3-propanediol, propylene carbonate, 1,4 cyclohexanedimethanol andmixtures thereof, said water soluble solvents being at a level that willnot form clear compositions by themselves. 15- A fabric softeningcomposition according to any one of claim 9-14, wherein said compositionis in a liquid form, preferably an aqueous dispersion. 16- A fabricsoftening composition according to claim 15, wherein said composition isa clear aqueous composition. 17- A fabric softening compositionaccording to either one of claim 14 or 15, wherein said composition hasa pH of from 3 to
 4. 18- A method of treating fabrics which comprisesthe step of contacting the fabrics in an aqueous medium containing thesoftener compound as defined in any one of claims 1-8 or the softeningcomposition as defined in any one of claims 9-17. 19- A method accordingto claim 18, wherein the fatty acid fraction/tertiary amine mole ratioin the softener compound is from 1.5:1 to less than 1.8:1, preferably1.5:1 and the aqueous medium comprises a molar ratio of anionicsurfactant to said softener compound of the invention of at least 1:10.20- A method according to claim 18, wherein the fatty acidfraction/tertiary amine mole ratio in the softener compound is from1.8:1 to 2:1, preferably 2:1 and the aqueous medium comprises a molarratio of anionic surfactant to said softener compound of the inventionof less than 1:10. 21- A premix composition comprising the fabricsoftener compound of any one of claims 1-8 and an effective amount of acomponent selected from the group consisting of principal solvents, lowmolecular weight water soluble solvents, water soluble calcium salt,water soluble magnesium salt, perfume, and mixtures thereof. 22- A solidfabric softener composition comprising an effective amount of the fabricsoftener active of any one of claims 1-8. 23- The process of making afabric softener composition comprising adding the premix of claim 21 towater, adjusting the pH to from 1.5 to 5, and adding an effective amountto improve viscosity and/or clarity of the composition, of water solublecalcium and/or magnesium salt. 24- A process for making a softenercompound which comprises the steps of: a)-reacting the fatty acidfraction comprising fatty acids of formula R¹COOH in which R¹ is a longchain C₅-C₂₁ branched alkyl or unsaturated alkyl, optionallysubstituted, with triethanolamine, in a molar ratio of fatty acidfraction to triethanolamine of from 1:1 to 2.5:1 for a period such thatthe condensation product obtained compound has an acid value, measuredby titration of the condensation product with a standard KOH solutionagainst a phenolphtaleine indicator, of less than 6.5, and b)-reactingthe condensation product thereby obtained with an alkylating agent, inthe presence or absence of a solvent. 25- A process according to claim24, wherein the alkylating agent is selected from alkyl halides,sulphates, phosphates and carbonates, preferably alkyl halides, morepreferably is dimethylsulfate.